A Universal and Straightforward Approach to Include Penetration Effects in Electrostatic Interaction Energy Estimation

Source abstract

Abstract To compensate for the lack of the explicit treatment of charge penetration in classical force fields, we propose a new charge‐distribution model based on a promolecule augmented with point charges (aug‐PROmol). It relies on a superposition of spherical atomic electron densities obtained for each chemical element from SCF energy optimized atomic orbitals. Atomic densities are further rescaled by partial point charges computed from fits to the molecular electrostatic potential. Aug‐PROmol was tested on the S66 benchmark dataset extended to nonequilibrium geometries ( J. Chem. Theory Comput., 2011, 7, 3466 ). The model does not need any additional parametrization other than point charges. Despite its simplicity, aug‐PROmol approximates the electrostatic energy with good agreement (RMSE=0.76 kcal mol −1 to DFT‐SAPT with B3LYP/aug‐cc‐pVTZ).